EP1606339B2 - Polymeric film or coating comprising xylan - Google Patents

Polymeric film or coating comprising xylan Download PDF

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Publication number
EP1606339B2
EP1606339B2 EP04721755.9A EP04721755A EP1606339B2 EP 1606339 B2 EP1606339 B2 EP 1606339B2 EP 04721755 A EP04721755 A EP 04721755A EP 1606339 B2 EP1606339 B2 EP 1606339B2
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European Patent Office
Prior art keywords
film
coating
films
polymeric film
xylan
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German (de)
French (fr)
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EP1606339A1 (en
EP1606339B1 (en
Inventor
Paul Gatenholm
Aase Bodin
Maria GRÖNDAHL
Sofia DAMMSTRÖM
Lisa Eriksson
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Seelution AB
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Seelution AB
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/14—Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/14—Hemicellulose; Derivatives thereof

Definitions

  • the present invention relates to a film-forming composition and a polymeric film or coating comprising hemicellulose. It also relates to the use of said film or coating as an oxygen barrier. Further, the invention relates to a method for the manufacture of a polymeric film or coating comprising hemicellulose, as well as to a method for improving the film-forming properties of hemicellulose.
  • EVOH Ethylene vinyl alcohol
  • PVOH polyvinyl alcohol
  • Hemicelluloses are polysaccharides that are biosynthesized in the majority of plants, where they act as a matrix material present between the cellulose microfibrils and as a linkage between lignin and cellulose. Hemicelluloses have been commercially used as sweetening agents, thickeners and emulsifiers in food. So far the non-food utilisation of hemicelluloses has been very limited. For example they have not yet been used commercially for the preparation of polymeric materials.
  • hemicellulose exhibit poor film-forming properties resulting in either fragmented or very brittle films.
  • the film-forming properties vary with the structure of the hemicellulose, which in turn is varying depending on its natural source and the extraction method. To be appropriate as a barrier material the film-forming properties have to be improved.
  • WO 02/06411 the use of heteroxylans for the preparation of a film-forming composition containing a plant protectant is disclosed.
  • the aim of WO 02/06411 is to provide a composition which is useful for applying a plant protectant to seeds or agricultural products.
  • the purpose of incorporating heteroxylans is to obtain a film-forming composition for the application of the plant protectant.
  • the molecular weight of the heteroxylans used in WO 02/06411 ranges from 100 000 to 250 000 g/mol.
  • the use of high molecular weight hemicellulose produces compositions having relatively high viscosities, which makes the compositions difficult to handle practically.
  • a biodegradable film is obtained by subjecting water-soluble hemicellulose to film-formation.
  • the hemicellulose used has an average molecular weight in the range of 50 000 to 1 000 000, preferably in the range of 100 000 to 400 000. Again, the high molecular weights present handling problems due to high viscosity.
  • the thickness of the films described in US Patent No 6 004 616 is 0,1 mm in dried state.
  • the films are relatively thick, which requires a lot of material to be consumed in the manufacture of the films. As a consequence thereof, the cost of materials will be very high.
  • the present invention provides a polymeric film or coating having a thickness of 10 ⁇ m or less, comprising xylan having a molecular weight from 20 000 to less than 50 000 g/mol, and at least one component selected from the group consisting of plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol, the content of plasticizer being in the range of 20-50% by dry weight.
  • plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol, the content of plasticizer being in the range of 20-50% by dry weight.
  • Another aspect of the invention concerns a method for the manufacture of a polymeric film or a coating having a thickness of 10 ⁇ m or less, comprising mixing xylan having a molecular weight from 20 000 to less than 50 000 g/mol with at least one component selected from the group consisting of plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol, the content of plasticizer being in the range of 20-50% by dry weight, and forming a film or coating.
  • plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol
  • One advantage with the present invention is the excellent oxygen barrier properties of the films or coatings produced.
  • the measured oxygen permeability was in the same range as for the commercial xylan and EVOH and for films of starch.
  • Another advantage of the present invention is that the mechanical properties of the films or coatings produced can be controlled by addition of various amounts or types of plasticizers, as defined above.
  • a further advantage is that the raw material in the present invention is renewable and can be extracted from biomass.
  • xylans having a molecular weight as defined above may be used for the purpose of preparing films which may be used as oxygen barriers.
  • xylans are used according to the present invention, since they are not so sensitive to humidity.
  • the xylans for use according to the invention have a molecular weight of of 20 000 to less than 50 000 g/mol.
  • molecular weights of the xylan are 20 000 - 48 000 g/mol, or in particular 20 000 - 45 000 g/mol or 20 000-40 000 g/mol.
  • the use of somewhat higher molecular weights facilitates film formation. If even higher molecular weights are used, high viscosity can complicate the use of the hemicellulose to produce a film or coating and the extraction methods are considerably restricted.
  • Xylans are present in biomass such as wood, cereals, grass and herbs and they are considered to be the second most abundant biopolymer in the plant kingdom. To separate xylans from other components in various sources of biomass, extraction with water and aqueous alkali can be used. Xylans are also commercially available from sources as Sigma Chemical Company.
  • Xylans may be divided into the sub-groups of heteroxylans and homoxylans.
  • the chemical structure of homoxylans and heteroxylans differs.
  • Homoxylans have a backbone of xylose residues and have some glucuronic acid or 4-O-methyl-glucuronic acid substituents.
  • Heteroxylans also have a backbone of xylose residues, but are in contrast to homoxylans extensively substituted not only with glucuronic acid or 4- O -methyl-glucuronic acid substituents but also with arabinose residues.
  • An advantage of homoxylans compaired to heteroxylans is that homoxylans crystallize to a higher extent. Crystallinity both decreases gas permeability and moisture sensitivity.
  • homoxylan which can be used according to the invention is glucuronoxylan.
  • heteroxylans which can be used according to the invention are arabinoxylan, glucuronoarabinoxylan and arabinoglucuronoxylan.
  • Xylans from any biomass or commercial source may be used to produce the films or coatings in the present invention.
  • film-formation is a necessary recruitment.
  • the films or coatings may be prepared by casting of an aqueous solution or dispersion comprising the xylan and the plasticizer.
  • aqueous solution or dispersion comprising the xylan and the plasticizer.
  • water is the most preferred solvent.
  • film refers to a separate sheet, which can be used e.g. for the packaging of food or pharmaceuticals.
  • coating refers to a covering that can be integrated in e.g. a carton in order to provide an oxygen barrier layer.
  • the film or coating according to the invention have a thickness of 10 micrometers or less.
  • the film or coating may have a thickness of 2 micrometers or 1 micrometer and still present the desired properties.
  • plasticizer as used herein relates to a substance of low molecular weight, which increases the flexibility of the material.
  • the plasticizer is selected from glycerol, xylitol, sorbitol and maltitol, ethylene glycol, propylene glycol, and butanediol.
  • the content of plasticizer is in the range of 20-50% by dry weight.
  • oxygen barrier used throughout this application is meant a material, which has low permeability to oxygen.
  • the oxygen barrier can be used to protect a substance, e.g. food or medicals, from exposure to oxygen.
  • the polymeric films or coatings according to the present invention can be used as an oxygen barrier in food packaging or pharmaceutical packaging.
  • films or coatings of the present invention can be used as an oxygen barrier layer on e.g. cartons and paper, possibly in combination with a water resistant material.
  • the films or coatings of the present invention can also be used for drug delivery, edible films and other polymeric applications.
  • This example illustrates the production of a film based on xylan, where the film-forming properties have been improved using the low molecular plasticizer xylitol.
  • a series of films containing 20 %, 27.5 %, 35 %, 42.5 % and 50 % of added xylitol (dry weight) were investigated.
  • a mixture of xylitol and glucoronoxylan from aspen with a total weight 1 g was solubilized in 35 ml of water in 95 °C for 15 minutes. The solution was then poured onto polystyrene Petri dishes with a diameter of 14 cm. After drying in 23 °C and 50 % RH for two to three days, transparent and more or less flexible films were obtained.
  • the molar mass of the glucuronoxylan was measured using size exclusion chromatography with 0.05 M LiBr in DMSO:water (90:10) as the mobile phase.
  • PSS Polymer Standard Service
  • the following PSS (Polymer Standard Service) column set was used: GRAM 30, 100, 3000 (8x300 mm) and guard column (8x50 mm).
  • the flow rate was 0.4 ml/min at 60 °C, resulting in a system pressure of 58 bar.
  • the samples were dissolved in the eluent in a shaker for 24 hours at room temperature and filtered using regenerated cellulose membranes (0.45 ⁇ m).
  • RI detector Shidex RI-71
  • Precision detectors PD 2000 Precision detectors PD 2000
  • Viscotek H502 Viscotek H502
  • the mechanical properties of the films were measured using a tensile testing machine (Lloyd L2000R) with a load cell of 100 N capacity.
  • the samples were cut into dog bone-shaped strips with a width of 1.5 cm.
  • the initial distance between the grips was 20 mm and the separation rate of the grips constant at 5 mm/min (Examples 1, 2 and 7) or 10 mm/min (Example 4). At least five replicates from each material were tested. For each sample the stress-strain curve was recorded and stress at break and strain at break were calculated.
  • the crystallinity of the films was investigated using wide angle x-ray scattering (WAXS). Films were milled to a fine powder using liquid nitrogen and the samples were investigated with a Siemens D5000 diffractometer. CuK ⁇ radiation was used with a wavelength of 1.54 ⁇ . 2 ⁇ was varied between 5° and 30°. Content of xylitol % Stress at break MPa Strain at break % O 2 - permeability (cm 3 ⁇ m)l (m 2 d kPa) 20 39.4 2.1 - 27.5 15.2 2.5 - 35 10.6 5.3 1.10 42.5 4.8 7.8 - 50 3.0 8.0 -
  • This example illustrates the production of a film based on xylan, where the film-forming properties have been improved using the low molecular plasticizer sorbitol.
  • the same procedure as in Example 1 was used except that sorbitol was used as plasticizer instead of xylitol and the series included three levels of plasticizers, namely 20 %, 35 % and 50 % was investigated.
  • This example illustrates the production of films made from xylan and polyvinyl alcohol.
  • the same procedure as in Example 1 was used but 0.75 g of polyvinyl alcohol (mw 20 000) was mixed with 0.25 g of xylan. Flexible films were formed. The measured oxygen permeability of the films was 0.18 (cm 3 ⁇ m) / (m 2 d kPa).
  • This example illustrates the production of films made from xylan and finely divided cellulose.
  • the resulting gel was poured onto a polystyrene Petri dish with a diameter of 14 cm, and dried at 50 °C for 48 h. After drying a flexible film was obtained.
  • the films produced according to this method exhibited a stress at break of 102.8 MPa, a strain at break of 3.1 % and an oxygen permeability of 0.225 (cm 3 ⁇ m) / (m 2 d kPa).
  • This example illustrates the production of a film based on xylan, where the xylan is obtained from an agricultural residue, such as oat spelts, barley husks or flax.
  • 1 g of arabinoxylan was solubilized in 35 ml of water in 95 °C for 15 minutes. The solution was then poured onto a polystyrene Petri dish with a diameter of 14 cm. After drying in 23 °C and 50 % RH for two to three days flexible films were obtained.
  • water is the preferred plasticizer.
  • the possibility to obtain films of arabinoxylan without the addition of any other plasticizer than water is very advantageous and a surprising aspect of the present invention.
  • the thickness of the films was 30-40 ⁇ m.
  • the molar mass of the arabinoxylan was measured using size exclusion chromatography as described in example 1. The obtained molar mass was 34 000 g/mol.
  • This example illustrates the production of a coating based on xylan.
  • a mixture of 0.105 g sorbitol and 0.195 g glucoronoxylan from aspen was solubilized in 30 ml of water in 95 °C for 15 minutes. The solution was then poured onto a plastic film in a polystyrene Petri dish with a diameter of 14 cm. After drying in 23 °C and 50 % RH for two to three days, a coating of xylan on the plastic film was obtained.
  • the molar mass of the glucuronoxylan was measured using size exclusion chromatography as described in example 1. The obtained molar mass was 15 000 g/mol.
  • the thickness of the coating was obtained by subtracting the thickness of the plastic film from the thickness of the plastic film with the xylan coating, measured using a micrometer. The obtained thickness of the coating was 1 micrometer.
  • This example illustrates the production of a film based on glucomannan, where the film-forming properties have been improved using the low molecular plasticizer sorbitol.
  • Films without sorbitol and films containing 20 % of added sorbitol (dry weight) were investigated.
  • a mixture of sorbitol and glucomannan with a total weight of 0.2 g was solubilized in 20 ml of water in 95 °C for 15 minutes. The solution was then poured onto polystyrene Petri dishes with a diameter of 9 cm. After drying in 23 °C and 50 % RH for two to three days, transparent and more or less flexible films were obtained.
  • the mechanical properties of the films were measured according to example 1.
  • the thickness of the samples, measured with a micrometer, was 60-70 ⁇ m. Content of sorbitol % Stress at break MPa Strain at break % 0 20.3 2.7 20 7.2 6.8

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Abstract

A film-forming composition and a polymeric film or coating comprising hemicellulose, having a molecular weight of less than 50 000 g/mol, and at least one component selected from the group consisting of plasticizers, cellulose and a synthetic oligomer or polymer is disclosed. The use of said film or coating as an oxygen barrier is also disclosed. Further, a method for the manufacture of said polymeric film or coating is disclosed, as well as a method for improving the film-forming properties of hemicellulose having a molecular weight of less than 50 000 g/mol.

Description

    Technical Field
  • The present invention relates to a film-forming composition and a polymeric film or coating comprising hemicellulose. It also relates to the use of said film or coating as an oxygen barrier. Further, the invention relates to a method for the manufacture of a polymeric film or coating comprising hemicellulose, as well as to a method for improving the film-forming properties of hemicellulose.
    • Background of the invention
  • The majority of plastic materials for packaging are today based on petroleum. However the fossil resources on the earth are limited. Incineration results in an increase of the greenhouse effect and furthermore these materials are in general not degradable. A sustainable development in the future requires a conversion to the use of renewable raw materials.
  • In many food packaging applications it is important to protect the food from oxygen as oxidation of aroma compounds, due to the ingress of oxygen, reduces the quality and the flavour of the product. This can be done by using a barrier material, which has low permeability to oxygen. Furthermore, it is desirable that the material is flexible, mechanically resistant, transparent and of low cost.
  • EVOH (Ethylene vinyl alcohol) and PVOH (polyvinyl alcohol) are examples of synthetic polymers exhibiting good barrier properties.
  • Lately, research has been made to obtain oxygen barriers based on renewable raw materials. Films based on proteins or polysaccharides, such as starch and cellulose, have shown to be good barriers for oxygen. One drawback of these materials is their sensitivity to water. When the surrounding relative humidity is increased the oxygen permeability increases as well.
  • Hemicelluloses are polysaccharides that are biosynthesized in the majority of plants, where they act as a matrix material present between the cellulose microfibrils and as a linkage between lignin and cellulose. Hemicelluloses have been commercially used as sweetening agents, thickeners and emulsifiers in food. So far the non-food utilisation of hemicelluloses has been very limited. For example they have not yet been used commercially for the preparation of polymeric materials.
  • The properties of films based on hemicellulose have so far been very seldom studied. In general, hemicellulose exhibit poor film-forming properties resulting in either fragmented or very brittle films. However, the film-forming properties vary with the structure of the hemicellulose, which in turn is varying depending on its natural source and the extraction method. To be appropriate as a barrier material the film-forming properties have to be improved.
  • In WO 02/06411 , the use of heteroxylans for the preparation of a film-forming composition containing a plant protectant is disclosed. The aim of WO 02/06411 is to provide a composition which is useful for applying a plant protectant to seeds or agricultural products. Thus, the purpose of incorporating heteroxylans is to obtain a film-forming composition for the application of the plant protectant.
  • The molecular weight of the heteroxylans used in WO 02/06411 ranges from 100 000 to 250 000 g/mol. The use of high molecular weight hemicellulose produces compositions having relatively high viscosities, which makes the compositions difficult to handle practically.
  • In US Patent No 6 004 616 a biodegradable film is obtained by subjecting water-soluble hemicellulose to film-formation. The hemicellulose used has an average molecular weight in the range of 50 000 to 1 000 000, preferably in the range of 100 000 to 400 000. Again, the high molecular weights present handling problems due to high viscosity.
  • Further, the thickness of the films described in US Patent No 6 004 616 is 0,1 mm in dried state. Thus, the films are relatively thick, which requires a lot of material to be consumed in the manufacture of the films. As a consequence thereof, the cost of materials will be very high.
  • There is thus a need for biodegradable film-forming compositions which overcome the abovementioned problems, and which presents the desired property of having low oxygen permeability.
    • Summary of the invention
  • The present invention provides a polymeric film or coating having a thickness of 10µm or less, comprising xylan having a molecular weight from 20 000 to less than 50 000 g/mol, and at least one component selected from the group consisting of plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol, the content of plasticizer being in the range of 20-50% by dry weight.
  • Another aspect of the invention concerns a method for the manufacture of a polymeric film or a coating having a thickness of 10µm or less, comprising mixing xylan having a molecular weight from 20 000 to less than 50 000 g/mol with at least one component selected from the group consisting of plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol, the content of plasticizer being in the range of 20-50% by dry weight, and forming a film or coating.
  • One advantage with the present invention is the excellent oxygen barrier properties of the films or coatings produced. The measured oxygen permeability was in the same range as for the commercial xylan and EVOH and for films of starch.
  • Another advantage of the present invention is that the mechanical properties of the films or coatings produced can be controlled by addition of various amounts or types of plasticizers, as defined above.
  • A further advantage is that the raw material in the present invention is renewable and can be extracted from biomass.
  • Materials based on biosynthesized polymers have several environmental advantages. After their use, these materials do not give rise to a net increase of carbon dioxide in the atmosphere and in addition most of them are biodegradable and as such can be disposed of by composting.
    • Detailed description of the invention
  • In the research work leading to the present invention it was shown that coherent films based on xylans exhibit excellent oxygen barrier properties. It has surprisingly been found that xylans having a molecular weight as defined above may be used for the purpose of preparing films which may be used as oxygen barriers. Xylans are used according to the present invention, since they are not so sensitive to humidity. The xylans for use according to the invention have a molecular weight of of 20 000 to less than 50 000 g/mol.
  • Other examples of molecular weights of the xylan are 20 000 - 48 000 g/mol, or in particular 20 000 - 45 000 g/mol or 20 000-40 000 g/mol. The use of somewhat higher molecular weights facilitates film formation. If even higher molecular weights are used, high viscosity can complicate the use of the hemicellulose to produce a film or coating and the extraction methods are considerably restricted.
  • Xylans are present in biomass such as wood, cereals, grass and herbs and they are considered to be the second most abundant biopolymer in the plant kingdom. To separate xylans from other components in various sources of biomass, extraction with water and aqueous alkali can be used. Xylans are also commercially available from sources as Sigma Chemical Company.
  • Xylans may be divided into the sub-groups of heteroxylans and homoxylans. The chemical structure of homoxylans and heteroxylans differs. Homoxylans have a backbone of xylose residues and have some glucuronic acid or 4-O-methyl-glucuronic acid substituents. Heteroxylans also have a backbone of xylose residues, but are in contrast to homoxylans extensively substituted not only with glucuronic acid or 4-O-methyl-glucuronic acid substituents but also with arabinose residues. An advantage of homoxylans compaired to heteroxylans is that homoxylans crystallize to a higher extent. Crystallinity both decreases gas permeability and moisture sensitivity.
  • An example of homoxylan which can be used according to the invention is glucuronoxylan.
  • Examples of heteroxylans which can be used according to the invention are arabinoxylan, glucuronoarabinoxylan and arabinoglucuronoxylan.
  • Xylans from any biomass or commercial source may be used to produce the films or coatings in the present invention. To obtain a coherent film, film-formation is a necessary recruitment.
  • The films or coatings may be prepared by casting of an aqueous solution or dispersion comprising the xylan and the plasticizer. Although other solvents could be used as solvents in the present invention, water is the most preferred solvent.
  • As used herein, the expression "film" refers to a separate sheet, which can be used e.g. for the packaging of food or pharmaceuticals.
  • As used herein, the expression "coating" refers to a covering that can be integrated in e.g. a carton in order to provide an oxygen barrier layer.
  • The film or coating according to the invention have a thickness of 10 micrometers or less.
  • It has surprisingly been found that very thin films may be made according to the present invention. For example, the film or coating may have a thickness of 2 micrometers or 1 micrometer and still present the desired properties.
  • The expression "plasticizer" as used herein relates to a substance of low molecular weight, which increases the flexibility of the material. The plasticizer is selected from glycerol, xylitol, sorbitol and maltitol, ethylene glycol, propylene glycol, and butanediol.
    The content of plasticizer is in the range of 20-50% by dry weight.
  • By the expression "oxygen barrier" used throughout this application is meant a material, which has low permeability to oxygen. The oxygen barrier can be used to protect a substance, e.g. food or medicals, from exposure to oxygen.
  • The polymeric films or coatings according to the present invention can be used as an oxygen barrier in food packaging or pharmaceutical packaging.
  • In addition, the films or coatings of the present invention can be used as an oxygen barrier layer on e.g. cartons and paper, possibly in combination with a water resistant material.
  • The films or coatings of the present invention can also be used for drug delivery, edible films and other polymeric applications.
    • Examples Example 1 (Reference Example not belonging to the Invention)
  • This example illustrates the production of a film based on xylan, where the film-forming properties have been improved using the low molecular plasticizer xylitol. A series of films containing 20 %, 27.5 %, 35 %, 42.5 % and 50 % of added xylitol (dry weight) were investigated. A mixture of xylitol and glucoronoxylan from aspen with a total weight 1 g was solubilized in 35 ml of water in 95 °C for 15 minutes. The solution was then poured onto polystyrene Petri dishes with a diameter of 14 cm. After drying in 23 °C and 50 % RH for two to three days, transparent and more or less flexible films were obtained.
  • The molar mass of the glucuronoxylan was measured using size exclusion chromatography with 0.05 M LiBr in DMSO:water (90:10) as the mobile phase. The following PSS (Polymer Standard Service) column set was used: GRAM 30, 100, 3000 (8x300 mm) and guard column (8x50 mm). The flow rate was 0.4 ml/min at 60 °C, resulting in a system pressure of 58 bar. The samples were dissolved in the eluent in a shaker for 24 hours at room temperature and filtered using regenerated cellulose membranes (0.45 µm). An RI detector (Shodex RI-71), a two-angle laser light scattering detector (Precision detectors PD 2000) and a viscosimetric detector (Viscotek H502) were used for detection. The data were collected and calculated using WINGPC 6.0 software of PSS. Molar mass data were calculated from the viscosity and RI signals by universal calibration using pullulan standards (PSS). The obtained molar mass was 15 000 g/mol.
  • The mechanical properties of the films were measured using a tensile testing machine (Lloyd L2000R) with a load cell of 100 N capacity. The samples were cut into dog bone-shaped strips with a width of 1.5 cm. The thickness of the samples, measured with a micrometer, was 30-40 µm. The initial distance between the grips was 20 mm and the separation rate of the grips constant at 5 mm/min (Examples 1, 2 and 7) or 10 mm/min (Example 4). At least five replicates from each material were tested. For each sample the stress-strain curve was recorded and stress at break and strain at break were calculated.
  • The oxygen permeability of the films was measured with a Mocon oxtran 2/20 equipment using a coulometric oxygen sensor. The area of the sample was 5 cm2 and the analysis was performed in 50 % RH. The oxygen permeability was calculated from the oxygen transmission and the measured thickness of the films and is presented in units of (cm3 µm) / (m2 d kPa), where d = 24 h.
  • The crystallinity of the films was investigated using wide angle x-ray scattering (WAXS). Films were milled to a fine powder using liquid nitrogen and the samples were investigated with a Siemens D5000 diffractometer. CuKα radiation was used with a wavelength of 1.54 Å. 2θ was varied between 5° and 30°.
    Content of xylitol % Stress at break MPa Strain at break % O2 -permeability (cm3 µm)l (m 2 d kPa)
    20 39.4 2.1 -
    27.5 15.2 2.5 -
    35 10.6 5.3 1.10
    42.5 4.8 7.8 -
    50 3.0 8.0 -
  • The flexibility increased with increasing amount of added plasticizer. All films were semi-crystalline and the degree of crystalliniy was little affected by the addition of xylitol.
    • Example 2 (Reference Example not belonging to the Invention)
  • This example illustrates the production of a film based on xylan, where the film-forming properties have been improved using the low molecular plasticizer sorbitol. The same procedure as in Example 1 was used except that sorbitol was used as plasticizer instead of xylitol and the series included three levels of plasticizers, namely 20 %, 35 % and 50 % was investigated.
    Content of sorbitol % Stress at break MPa Strain at break % O2-permeability (cm3 µm)/ (m2 d kPa)
    20 35.4 2.0 -
    35 13.5 5.8 0.21
    50 3.9 10.4 -
  • The flexibility of the films increased with increasing amount of sorbitol. The addition of sorbitol had only a minor effect on the relative crystallinity of the films.
    • Example3 (Reference Example not belonging to the Invention)
  • This example illustrates the production of films made from xylan and polyvinyl alcohol. The same procedure as in Example 1 was used but 0.75 g of polyvinyl alcohol (mw 20 000) was mixed with 0.25 g of xylan. Flexible films were formed. The measured oxygen permeability of the films was 0.18 (cm3 µm) / (m2 d kPa).
    • Example 4 (Reference Example not belonging to the Invention)
  • This example illustrates the production of films made from xylan and finely divided cellulose. 0.37 g of glucuronoxylan, solubilized in 20 ml of water in 95 °C for 15 minutes, was added to 1.13 g of bacterial cellulose homogenized in 120 ml of water. The blend was allowed to interact for 30 minutes. The resulting gel was poured onto a polystyrene Petri dish with a diameter of 14 cm, and dried at 50 °C for 48 h. After drying a flexible film was obtained. The films produced according to this method exhibited a stress at break of 102.8 MPa, a strain at break of 3.1 % and an oxygen permeability of 0.225 (cm3 µm) / (m2 d kPa).
    • Example 5 (Reference Example not belonging to the Invention)
  • This example illustrates the production of a film based on xylan, where the xylan is obtained from an agricultural residue, such as oat spelts, barley husks or flax. 1 g of arabinoxylan was solubilized in 35 ml of water in 95 °C for 15 minutes. The solution was then poured onto a polystyrene Petri dish with a diameter of 14 cm. After drying in 23 °C and 50 % RH for two to three days flexible films were obtained.
  • In this case, water is the preferred plasticizer. The possibility to obtain films of arabinoxylan without the addition of any other plasticizer than water is very advantageous and a surprising aspect of the present invention.
  • The thickness of the films, measured with a micrometer, was 30-40 µm.
  • The molar mass of the arabinoxylan was measured using size exclusion chromatography as described in example 1. The obtained molar mass was 34 000 g/mol.
  • The oxygen permeability of the films was measured with a Mocon oxtran 2/20 equipment using a coulometric oxygen sensor. The area of the sample was 5 cm2 and the analysis was performed in 50 % RH. The oxygen permeability, calculated from the oxygen transmission and the measured thickness of the films, was 0.19 (cm3 µm) / (m2 d kPa), where d = 24 h.
    • Example 6 (Reference Example not belonging to the Invention)
  • This example illustrates the production of a coating based on xylan. A mixture of 0.105 g sorbitol and 0.195 g glucoronoxylan from aspen was solubilized in 30 ml of water in 95 °C for 15 minutes. The solution was then poured onto a plastic film in a polystyrene Petri dish with a diameter of 14 cm. After drying in 23 °C and 50 % RH for two to three days, a coating of xylan on the plastic film was obtained.
  • The molar mass of the glucuronoxylan was measured using size exclusion chromatography as described in example 1. The obtained molar mass was 15 000 g/mol.
  • The thickness of the coating was obtained by subtracting the thickness of the plastic film from the thickness of the plastic film with the xylan coating, measured using a micrometer. The obtained thickness of the coating was 1 micrometer.
    • Example 7 (Reference Example not belonging to the Invention)
  • This example illustrates the production of a film based on glucomannan, where the film-forming properties have been improved using the low molecular plasticizer sorbitol. Films without sorbitol and films containing 20 % of added sorbitol (dry weight) were investigated. A mixture of sorbitol and glucomannan with a total weight of 0.2 g was solubilized in 20 ml of water in 95 °C for 15 minutes. The solution was then poured onto polystyrene Petri dishes with a diameter of 9 cm. After drying in 23 °C and 50 % RH for two to three days, transparent and more or less flexible films were obtained.
  • The mechanical properties of the films were measured according to example 1. The thickness of the samples, measured with a micrometer, was 60-70 µm.
    Content of sorbitol % Stress at break MPa Strain at break %
    0 20.3 2.7
    20 7.2 6.8
  • The flexibility increased with addition of plasticizer.

Claims (9)

  1. A polymeric film or coating having a thickness of 10µm or less, comprising xylan having a molecular weight from 20 000 to less than 50 000 g/mol, and at least one component selected from the group consisting of plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol, the content of plasticizer being in the range of 20-50% by dry weight.
  2. A polymeric film or coating according to claim 1, wherein said xylan is a homoxylan.
  3. A polymeric film or coating according to claim 2, wherein said homoxylan is glucuronoxylan.
  4. A polymeric film or coating according to claim 1, wherein said xylan is a heteroxylan.
  5. A polymeric film or coating according to claim 4, wherein said heteroxylan is selected from the group consisting of arabinoxylan, glucuronoarabinoxylan and arabinoglucuronoxylan.
  6. A polymeric film or coating according to any one of the preceding claims, wherein said plasticizer is sorbitol.
  7. A polymeric film or coating according to any one of the claims 1 to 5, wherein said plasticizer is xylitol.
  8. Use of a polymeric film or coating according to any one of the preceding claims as an oxygen barrier.
  9. A method for the manufacture of a polymeric film or a coating having a thickness of 1µm or less, comprising mixing xylan having a molecular weight from 20 000 to less than 50 000 g/mol with at least one component selected from the group consisting of plasticizers selected from glycerol, xylitol, sorbitol, maltitol, ethylene glycol, propylene glycol and butanediol, the content of plasticizer being in the range of 20-50% by dry weight, and forming a film or coating.
EP04721755.9A 2003-03-21 2004-03-18 Polymeric film or coating comprising xylan Expired - Lifetime EP1606339B2 (en)

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PCT/SE2004/000413 WO2004083286A1 (en) 2003-03-21 2004-03-18 Polymeric film or coating comprising hemicellulose

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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006017787A2 (en) * 2004-08-06 2006-02-16 Grain Processing Corporation Tablet coating composition
NO20065147L (en) * 2006-11-08 2008-05-09 Ntnu Tech Transfer As Nanocomposites based on cellulose whiskers and cellulose plastic
SE0700404L (en) * 2007-02-19 2008-08-20 Xylophane Ab Polymeric film or coating comprising hemicellulose
FI121811B (en) * 2007-06-01 2011-04-29 Upm Kymmene Corp New dispersions and processes for their preparation
DE602007008591D1 (en) † 2007-11-27 2010-09-30 Innventia Ab Use of a wood hydrolyzate
US8198219B2 (en) 2008-02-22 2012-06-12 Basf Se Method for producing solid materials on the basis of synthetic polymers and/or biopolymers and use thereof
US8772406B2 (en) * 2009-08-06 2014-07-08 Robert J. Linhardt Synthetic wood composite
US9637561B2 (en) 2011-02-08 2017-05-02 Advanced Polymer Technology Ab Plasticizer-free flexible oxygen barrier films and laminates based on negatively charged and acetylated non-cellulosic polysaccharides isolated from biomass
EP2705099A4 (en) * 2011-05-04 2015-07-01 Kth Holding Ab Oxygen barrier for packaging applications
DE212012000194U1 (en) 2011-10-31 2014-06-11 Xylophane Aktiebolag A migration barrier film or coating comprising hemicellulose
SE1250261A1 (en) * 2011-10-31 2013-05-01 Billerudkorsnaes Gaevle Froevi Ab Coating composition, a method for coating a substrate, a coated substrate, a packaging material and liquid packaging
CN102775647B (en) * 2012-07-30 2014-07-30 昆明理工大学 Preparation method of hemicellulose based edible film
JP6043693B2 (en) * 2012-10-19 2016-12-14 富士フイルム株式会社 Protective film forming resin composition, protective film, pattern forming method, electronic device manufacturing method, and electronic device
CN103382677B (en) * 2013-07-25 2015-11-04 海南必凯水性涂料有限公司 A kind of high-barrier polyvinyl alcohol coating for internal lining paper coating and preparation method thereof
WO2015126468A1 (en) * 2014-02-19 2015-08-27 Celanese Acetate Llc Hemicellulose compositions
SG10202107085TA (en) 2015-04-10 2021-08-30 Comet Biorefining Inc Methods and compositions for the treatment of cellulosic biomass and products produced thereby
DE102016201498B4 (en) * 2016-02-01 2017-08-17 Norbert Kuhl OXYGEN-CONTAINED FOOD CONTAINER
CN106497085A (en) * 2016-11-03 2017-03-15 金福英 A kind of edible package film and preparation method thereof
DE102017211562B4 (en) * 2017-07-06 2021-12-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Coated cellulose fiber, process for its production, fiber-reinforced composite material, process for its production and its use
EA202092695A1 (en) 2018-05-10 2021-02-25 Комет Байорифайнинг Инк. COMPOSITIONS CONTAINING GLUCOSE AND HEMICELLULOSE AND THEIR APPLICATION
CN110078883B (en) * 2019-05-22 2021-08-03 西华大学 Water-based paint resin based on konjac flour, preparation method and composition thereof
SE544369C2 (en) * 2020-06-30 2022-04-26 Stora Enso Oyj Barrier Coating for Paper and Paperboard
SE545615C2 (en) * 2021-06-09 2023-11-14 Stora Enso Oyj Barrier coating comprising a first and a second polysaccharide for paper and paperboard, coated substrate and method for the production thereof
CN115466414B (en) * 2022-01-25 2023-08-01 北京林业大学 Preparation method of hemicellulose-based plastic
WO2024157029A1 (en) 2023-01-26 2024-08-02 Sun Chemical B.V. Dehazing coatings and method for use

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419316A (en) * 1974-07-10 1983-12-06 Schweiger Richard Georg Process of making films, fibers or other shaped articles consisting of, or containing, polyhydroxy polymers
CA1167403A (en) * 1979-07-10 1984-05-15 Unilever Limited Microbial heteropolysaccharide
US4564649A (en) * 1984-04-16 1986-01-14 H. B. Fuller Company Polyvinyl alcohol and lignin sulfonate containing adhesive
JPS61152765A (en) * 1984-12-27 1986-07-11 Nippon Ekishiyou Kk Synthetic resin product including compound clathrated with cyclodextrin
US5095054A (en) * 1988-02-03 1992-03-10 Warner-Lambert Company Polymer compositions containing destructurized starch
US5179021A (en) * 1989-02-10 1993-01-12 Gil Inc. (Now Ici Canada Inc.) Pulp bleaching process comprising oxygen delignification and xylanase enzyme treatment
US5089307A (en) * 1989-05-23 1992-02-18 Mitsubishi Rayon Co., Ltd. Edible film and method of making same
US6004616A (en) * 1990-02-07 1999-12-21 Fuji Oil Company, Ltd. Biodegradable vegetable film
JPH04331246A (en) 1991-04-10 1992-11-19 Goyo Paper Working Co Ltd Gas barrier material and container material produced therefrom
US5468287A (en) * 1992-11-02 1995-11-21 Fuji Oil Co., Ltd. Water color
FR2701956B1 (en) * 1993-02-26 1995-05-24 Sais Process for manufacturing flexible, solid, biodegradable films, and products obtained.
US5646206A (en) * 1993-04-23 1997-07-08 The United States Of America As Represented By The Secretary Of Agriculture Films fabricated from mixtures of pectin and poly(vinyl alchohol)
FR2728259B1 (en) 1994-12-14 1997-03-14 Rhone Poulenc Chimie PROCESS FOR HEMIHYDROGENATION OF DINITRILES IN AMINONITRILES
FR2730236B1 (en) 1995-02-08 1997-04-18 Generale Sucriere Sa PROCESS FOR THE DEVELOPMENT OF BEET PULP, IN PARTICULAR FOR PREPARING ADHESIVES, COATING PRODUCTS, OR ADHESIVE FILMS REVERSIBLE WITH WATER
DE19517034A1 (en) * 1995-05-10 1996-11-14 Hoechst Ag Use of inclusion compounds of ring-shaped polysaccharides as charge control agents
ZA974084B (en) * 1996-05-10 1998-02-23 Danisco Novel α-glucuronidases, production hereof and their uses.
US6057438A (en) * 1996-10-11 2000-05-02 Eastman Chemical Company Process for the co-production of dissolving-grade pulp and xylan
FR2779638B1 (en) * 1998-06-15 2000-08-04 Oreal COSMETIC COMPOSITION CONTAINING A POLYSACCHARIDE AND AN ACRYLIC TERPOLYMER AND USE OF THIS COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS
US6352845B1 (en) * 1999-02-10 2002-03-05 Eastman Chemical Company Corn fiber for the production of advanced chemicals and materials: separation of monosaccharides and methods thereof
US6191196B1 (en) * 1999-04-12 2001-02-20 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polymer compositions, methods for making same and articles therefrom
EP1095977A1 (en) * 1999-10-28 2001-05-02 Ucb, S.A. Water based polymer composition comprising a biopolymer and a polymer resin
US6395204B1 (en) * 2000-01-28 2002-05-28 Weyerhaeuser Company Plastic wood, method of processing plastic wood, and resulting products
EP1134232A1 (en) * 2000-03-16 2001-09-19 SCA Hygiene Products AB Polysaccharide-based superabsorbent film
CN1119932C (en) * 2000-07-07 2003-09-03 中国科学院生态环境研究中心 Biological seed coating agent
FR2811998B1 (en) * 2000-07-18 2003-08-29 Ulice USE OF HETEROXYLANES FOR THE PREPARATION OF FILM-FORMING COMPOSITIONS
US20020107303A1 (en) * 2000-10-12 2002-08-08 Seiko Epson Corporation Method of preparation of polymer emulsion and ink composition comprising the polymer emulsion
SE0101096D0 (en) * 2001-03-28 2001-03-28 Polysaccharide Ind Ab Protective coating
US6946506B2 (en) * 2001-05-10 2005-09-20 The Procter & Gamble Company Fibers comprising starch and biodegradable polymers
US6878760B2 (en) * 2001-09-14 2005-04-12 The Goodyear Tire & Rubber Company Preparation of starch reinforced rubber and use thereof in tires
FR2829142B1 (en) * 2001-12-27 2004-02-13 Ulice FILMOGENEOUS COMPOSITION OF HETEROXYLANE FOR THE MANUFACTURE OF CAPSULES THUS OBTAINED
EP1465944B1 (en) * 2002-01-16 2015-02-25 Eastman Chemical Company Novel carbohydrate esters and polyol esters as plasticizers for polymers, compositions and articles including such plasticizers and methods of using the same
DE10208858A1 (en) * 2002-03-01 2003-09-11 Kalle Gmbh & Co Kg Smoke and water vapor permeable food casing made of a thermoplastic mixture
AU2003277105A1 (en) * 2002-10-01 2004-04-23 The Procter And Gamble Company Strengthened tissue paper products comprising low levels of xylan
FI20021772A (en) * 2002-10-04 2004-04-05 Biotie Therapies Oyj Novel carbohydrate compositions and process for their preparation
US20040259218A1 (en) * 2003-05-06 2004-12-23 Weimer Paul J. Wood adhesives containing solid residues of biomass fermentations
US7666946B2 (en) * 2006-01-27 2010-02-23 Arkema Inc. Blends of biopolymers with acrylic copolymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. Gründahl, "Effect of Molecular Architecture of Xylan on Material Properties",Licentiate essay presented and published in relation to a seminar June 5 2003 atChalmers University of Technology, including three papers †

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US20060173104A1 (en) 2006-08-03
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CA2516612C (en) 2012-06-26
DE602004015263D1 (en) 2008-09-04
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PT1606339E (en) 2008-10-22
AU2004221959A1 (en) 2004-09-30
US7427643B2 (en) 2008-09-23
SE0300801D0 (en) 2003-03-21
CN1761703A (en) 2006-04-19
BRPI0408511B1 (en) 2016-03-22
CA2516612A1 (en) 2004-09-30
DK1606339T4 (en) 2017-05-01

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